Photoresist compositions, intermediate products, and methods of manufacturing patterned devices and semiconductor devices

ABSTRACT

A photoresist composition includes a photoresist polymer including a repeating unit to which a silicon-containing leaving group is combined, a photo-fluorine generator including a sulfonium fluoride, and a solvent.

CROSS-REFERENCE TO RELATED APPLICATION

This a Continuation of U.S. application Ser. No. 15/372,773, filed Dec.8, 2015, in which a claim of priority under 35 USC § 119 is made toKorean Patent Application No. 10-2015-0175067, filed on Dec. 9, 2015, inthe Korean Intellectual Property Office (KIPO), the content of which isincorporated by reference herein in its entirety.

BACKGROUND

Example embodiments relate to photoresist compositions, intermediateproducts having photoresistive layers, and to methods of manufacturingpatterned devices and semiconductor devices. More particularly, exampleembodiments relate to photoresist compositions including aphotosensitive polymer, to intermediate products having photoresistivelayers including a photoresistive polymer, and to methods ofmanufacturing patterned devices and semiconductor devices usingphotoresist compositions including a photosensitive polymer.

Photolithography processes are utilized to form material layer patternsin semiconductor devices. In one type of photolithography process, aphotoresist layer is partially exposed in an exposure process (e.g., bya light source) to define an exposed portion and a non-exposed portionof the photoresist layer, and then either the exposed portion or thenon-exposed portion is removed in a developing process to form aphotoresist pattern. An object layer underlying the photoresist patternmay be etched using the photoresist pattern as an etching mask to form adesired pattern in the object layer.

SUMMARY

According to an aspect of the inventive concepts, there is provided aphotoresist composition that includes a photoresist polymer including arepeating unit to which a silicon-containing leaving group is combined,a photo-fluorine generator including a sulfonium fluoride, and asolvent.

According to another aspect of the inventive concepts, there is provideda photoresist composition that includes a photoresist polymer includinga repeating unit to which a silicon-containing leaving group iscombined, a photo-fluorine generator, a sensitizer capable of generatingfluorine, and a solvent.

According to still another aspect of the inventive concepts, there isprovided a method of manufacturing a patterned device. In the method, anobject layer is formed on a substrate. A photoresist layer is formed onthe object layer by coating the object layer with a photoresistcomposition. The photoresist composition includes a photoresist polymerincluding a repeating unit to which a silicon-containing leaving groupis combined, a photo-fluorine generator including a sulfonium fluorideand a solvent. An exposure process is performed on the photoresist layersuch that the photoresist layer may be divided into an exposed portionand a non-exposed portion. The exposed portion is removed to form aphotoresist pattern. The object layer is patterned using the photoresistpattern.

According to yet another aspect of the inventive concepts, there isprovided a method of manufacturing a semiconductor device. In themethod, an isolation layer is formed on a substrate to define activepatterns on the substrate. A gate structure is formed on the isolationlayer and the active patterns. Contacts electrically connected to theactive patterns are formed. An insulating interlayer covering the gatestructure and the contacts is formed. A photoresist layer is formed onthe insulating interlayer by coating the insulating layer with aphotoresist composition. The photoresist composition includes aphotoresist polymer including a repeating unit to which asilicon-containing leaving group is combined, a photo-fluorine generatorincluding a sulfonium fluoride, and a solvent. The photoresist layer ispartially removed to form a photoresist pattern. The insulatinginterlayer is partially etched using the photoresist pattern as a maskto form openings through which the contacts are exposed. Wirings areformed in the openings to be electrically connected to the contacts.

According to another aspect of the inventive concepts, an intermediateproduct is provided which includes a semiconductor substrate, an objectlayer on the semiconductor layer, and a photoresistive layer on theobject layer. The photoresistive layer includes a photoresistivecompound, and the photoresistive compound includes a photoresist polymerincluding a repeating unit to which a silicon-containing leaving groupis combined, a photo-fluorine generator including a sulfonium fluoride,and a solvent.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other aspects of the inventive concepts will becomereadily apparent from the detailed description that follows taken inconjunction with the accompanying drawings which represent non-limiting,example embodiments as described herein.

FIGS. 1 to 6 are cross-sectional views for reference in describing amethod of forming a pattern in accordance with example embodiments;

FIGS. 7 to 13 cross-sectional views for reference in describing a methodof manufacturing a patterned device in accordance with exampleembodiments; and

FIGS. 14 to 35 are top plan views and cross-sectional views forreference in describing a method of manufacturing a semiconductor devicein accordance with example embodiments.

DESCRIPTION OF EMBODIMENTS

Various example embodiments will be described more fully hereinafterwith reference to the accompanying drawings, in which some exampleembodiments are shown. The present inventive concept may, however, beembodied in many different forms and should not be construed as limitedto the example embodiments set forth herein. Rather, these exampleembodiments are provided so that this description will be thorough andcomplete, and will fully convey the scope of the present inventiveconcept to those skilled in the art. In the drawings, the sizes andrelative sizes of layers and regions may be exaggerated for clarity.

It will be understood that when an element or layer is referred to asbeing “on,” “connected to” or “coupled to” another element or layer, itcan be directly on, connected or coupled to the other element or layeror intervening elements or layers may be present. In contrast, when anelement is referred to as being “directly on,” “directly connected to”or “directly coupled to” another element or layer, there are nointervening elements or layers present. Like numerals refer to likeelements throughout. As used herein, the term “and/or” includes any andall combinations of one or more of the associated listed items.

It will be understood that, although the terms first, second, third,fourth etc. may be used herein to describe various elements, components,regions, layers and/or sections, these elements, components, regions,layers and/or sections should not be limited by these terms. These termsare only used to distinguish one element, component, region, layer orsection from another region, layer or section. Thus, a first element,component, region, layer or section discussed below could be termed asecond element, component, region, layer or section without departingfrom the teachings of the present inventive concept.

Spatially relative terms, such as “beneath,” “below,” “lower,” “above,”“upper” and the like, may be used herein for ease of description todescribe one element or feature's relationship to another element(s) orfeature(s) as illustrated in the figures. It will be understood that thespatially relative terms are intended to encompass differentorientations of the device in use or operation in addition to theorientation depicted in the figures. For example, if the device in thefigures is turned over, elements described as “below” or “beneath” otherelements or features would then be oriented “above” the other elementsor features. Thus, the exemplary term “below” can encompass both anorientation of above and below. The device may be otherwise oriented(rotated 90 degrees or at other orientations) and the spatially relativedescriptors used herein interpreted accordingly.

The terminology used herein is for the purpose of describing particularexample embodiments only and is not intended to be limiting of thepresent inventive concept. As used herein, the singular forms “a,” “an”and “the” are intended to include the plural forms as well, unless thecontext clearly indicates otherwise. It will be further understood thatthe terms “comprises” and/or “comprising,” when used in thisspecification, specify the presence of stated features, integers, steps,operations, elements, and/or components, but do not preclude thepresence or addition of one or more other features, integers, steps,operations, elements, components, and/or groups thereof.

Example embodiments are described herein with reference tocross-sectional illustrations that are schematic illustrations ofidealized example embodiments (and intermediate structures). As such,variations from the shapes of the illustrations as a result, forexample, of manufacturing techniques and/or tolerances, are to beexpected. Thus, example embodiments should not be construed as limitedto the particular shapes of regions illustrated herein but are toinclude deviations in shapes that result, for example, frommanufacturing. For example, an implanted region illustrated as arectangle will, typically, have rounded or curved features and/or agradient of implant concentration at its edges rather than a binarychange from implanted to non-implanted region. Likewise, a buried regionformed by implantation may result in some implantation in the regionbetween the buried region and the surface through which the implantationtakes place. Thus, the regions illustrated in the figures are schematicin nature and their shapes are not intended to illustrate the actualshape of a region of a device and are not intended to limit the scope ofthe present inventive concept.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this inventive concept belongs. Itwill be further understood that terms, such as those defined in commonlyused dictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art andwill not be interpreted in an idealized or overly formal sense unlessexpressly so defined herein.

Although corresponding plan views and/or perspective views of somecross-sectional view(s) may not be shown, the cross-sectional view(s) ofdevice structures illustrated herein provide support for a plurality ofdevice structures that extend along two different directions as would beillustrated in a plan view, and/or in three different directions aswould be illustrated in a perspective view. The two different directionsmay or may not be orthogonal to each other. The three differentdirections may include a third direction that may be orthogonal to thetwo different directions. The plurality of device structures may beintegrated in a same electronic device. For example, when a devicestructure (e.g., a memory cell structure or a transistor structure) isillustrated in a cross-sectional view, an electronic device may includea plurality of the device structures (e.g., memory cell structures ortransistor structures), as would be illustrated by a plan view of theelectronic device. The plurality of device structures may be arranged inan array and/or in a two-dimensional pattern.

A photoresist composition in accordance with example embodiments may beutilized in a photo-lithography process for forming, for example, aninsulation pattern, a gate electrode and/or a wiring structure includedin a semiconductor device. In some example embodiments, the photoresistcomposition may exhibit sensitivity to an extreme ultraviolet (EUV)light source.

In example embodiments, the photoresist composition includes aphotoresist polymer, a photo-fluorine generator and a solvent. In someother example embodiments, the photoresist composition further includesa sensitizer.

A fluorine-ion (F⁻) may be generated through a reaction between thephoto-fluorine generator and a photon created from, for example, the EUVlight source.

In example embodiments, the photo-fluorine generator includes asulfonium fluoride in which a sulfonium ion and the fluorine ion as acounter ion may be combined.

For example, a structure of the photo-fluorine generator may berepresented by the following Chemical Formula 1.

In the Chemical Formula 1 above, R₁, R₂ and R₃ may be independentlyhydrogen, a C1-C20 aliphatic hydrocarbon group, or a C1-C20 heteroaliphatic hydrocarbon group including at least one of nitrogen (N),oxygen (O) or halogen. Here and throughout this disclosure, the term“independently” means that the selection of one element or constituentis not dependent upon the selection of the other elements orconstituents. Accordingly, none, some or all of the listed elements orconstituents may be the same as each other. For example, the case ofChemical Formula 1, all of R₁, R₂ and R₃ can be the same as each other,two of R₁, R₂ and R₃ can be the same as each other, or none of R₁, R₂and R₃ can be the same as each other.

In the sulfonium ion, a rearrangement reaction may occur in at least oneof phenyl rings combined to sulfur (S) through a photo-chemical reactionwith a photon. A proton (H⁺) may be generated from the sulfonium ion byan electron transfer derived from the rearrangement reaction. The protonmay be combined with the fluorine ion to create fluoric acid (HF).

As described above, the sulfonium ion may be stabilized by therearrangement reaction, so that a generation of the fluorine ion or HFmay be facilitated even by a relatively small quantity of photons.

In example embodiments, the photoresist polymer may include a repeatingunit that may be combined to a back-bone chain and may include asilicon-containing leaving group.

The back-bone chain may include a carbon chain included in a photoresistmaterial. For example, the back-bone chain may include a polymer chainsuch as novolak, polystyrene, polyhydroxystyrene (PHS), polyacrylate,polymethacrylate, polyvinyl ester, polyvinyl ether, polyolefin,polynorbornene, polyester, polyamide, polycarbonate or the like. Inexample embodiments, novolak, polystyrene, PHS or polyacrylate are usedas the back-bone chain.

The silicon-containing leaving group may include, for example, a silylgroup. For example, the silicon-containing leaving group may includetrimethyl silyl (TMS), tert-butyl dimethyl silyl (TBDMS), triisopropylsilyl (TIPS), tert-butyl diphenyl silyl (TBDPS) or a combinationthereof.

The silicon-containing leaving group may be combined to the back-bonechain via a linker group. In some embodiments, the linker group mayinclude an ester group.

For example, a structure of the repeating unit including thesilicon-containing leaving group may be represented by the followingChemical Formula 2 or Chemical Formula 3.

In the Chemical Formulae 2 and 3 above, R₄, R₅ and R₆ may beindependently hydrogen, a C1-C20 alkyl group, a C3-C20 cycloalkyl groupor a C6-C30 aromatic group. R₄, R₅ and R₆ may be the same as ordifferent from each other. X of Chemical Formula 3 may represent adivalent group selected from styrene, hydroxystyrene, acrylate, benzene,hydroxybenzene, C1-C6 alkylene, C6-C30 arylene, carbonyl, oxy, a C2-C30unsaturated aliphatic group or a combination thereof. Consistent withthe definition of “independently” previously set forth, two or more ofR₄, R₅ and R₆ may be the same as each other, or R₄, R₅ and R₆ may all bedifferent from each other. R₉ may be hydrogen or methyl group.

In example embodiments, a fluorine ion (F⁻) may be generated from HFformed by the photo-fluorine generator. The fluorine ion may attack asilicon atom of the repeating unit that may include thesilicon-containing leaving group so that the silicon-containing leavinggroup may be separated or deprotected from the repeating unit. A proton(H⁺) generated from HF may be trapped at a site from which thesilicon-containing group may be separated to create a hydroxyl group ora carboxyl group. Thus, an exposed portion of the photoresist polymermay have increased hydrophilicity and/or polarity.

In some example embodiments, the silicon-containing leaving group iscombined with at least two linker groups. For example, thesilicon-containing leaving group may be connected to two ester groups.

In this case, a structure of the repeating unit including thesilicon-containing leaving group may be represented by the followingChemical Formula 4.

In the Chemical Formula 4 above, R₇ and R₈ may be independentlyhydrogen, a C1-C20 alkyl group, a C3-C20 cycloalkyl group or a C6-C30aromatic group, and n may represent a natural number of 1 to 20. R₁₀ andR₁₁ may be independently hydrogen or methyl group. Consistent with thedefinition of “independently” previously set forth, R₇ and R₈ may be thesame as or different from each other.

As described above, the fluorine ion generated from the photo-fluorinegenerator may attack a silicon atom of the repeating unit represented byChemical Formula 4 to create two hydroxyl groups or carboxylic groups.Thus, hydrophilicity and/or polarity of the exposed portion may befurther increased.

The sensitizer may be added to amplify the number of the fluorine ionsby photons introduced from the light source.

In example embodiments, the sensitizer includes an aromatic compoundincluding a fluorine substituent. In some other example embodiments, thesensitizer further includes a substituent containing an unsharedelectron pair.

In some example embodiments, the structure of the sensitizer isrepresented by the following Chemical Formula 5.

In the Chemical Formula 5 above, F represents the fluorine substituent.The number of the fluorine substituents may be an integer between 1 and5 both inclusive. Y represents the substituent containing the unsharedelectron pair, and may include a hydroxyl group, an alkoxy group, athiol group or an amino group.

In some embodiments, the sensitizer may be represented by the followingChemical Formula 6.

When the sensitizer is exposed to the photons from the light source, forexample, resonance stabilization structures may be formed by theunshared electron pair included in the hydroxyl group and a benzenering. A secondary electron may be created by the resonance stabilizationto release a fluorine ion.

In some example embodiments, a plurality of the fluorine ions arereleased from one molecular of the sensitizer. Therefore, sensitivity ina photo-lithography process utilizing the photoresist composition may befurther enhanced.

In some example embodiments, the sensitizer is coupled to the back-bonechain of the photoresist polymer as a sensitizer repeating unit. Thesensitizer repeating unit may include one to four fluorine substituents.For example, the sensitizer repeating unit may be represented by thefollowing Chemical Formula 7.

The solvent may include an organic solvent exhibiting favorablesolubility for a polymer material, and a favorable coatability (e.g.,good coating characteristics) for formation of a uniform photoresistlayer. Nonlimiting examples of the solvent include cyclohexanone,cyclopentanone, tetrahydrofuran (THF), dimethylformamide, propyleneglycol monomethyl ether acetate (PGMEA), ethyl lactate, methyl ethylketone, benzene or toluene. These may be used alone or in a combinationof two or more thereof.

The photoresist composition may further include an additive forimproving chemical and physical properties of a photoresist layer formedfrom the photoresist composition. The additive may include, for example,a surfactant, a leveling agent, a viscosity modifier, and so on.

In example embodiments, the photoresist composition includes thephotoresist polymer in a range from about 5 weight percent (wt %) toabout 20 wt %, the photo-fluorine generator in a range from about 0.1 wt% to about 5 wt %, the sensitizer in a range from about 0.01 wt % toabout 1 wt %, the additive in a range from about 0.01 wt % to about 1 wt%, and the solvent in a range from about 75 wt % to about 94 wt %, basedon a total weight of the composition. However, the inventive conceptsare not limited to these composition ranges.

In example embodiments, the photoresist composition does not include aphoto-acid generator (PAG). In this case, defects of a photoresistpattern caused by an irregular diffusion of an acid from the PAG may besubstantially prevented or reduced.

The photoresist composition according to example embodiments may bereferred to as a positive-type composition. For example, when theexposure process may be performed on the photoresist layer formed fromthe composition, an active fluorine such as a fluorine ion may begenerated from the photo-fluorine generator at an exposed portion. Thesilicon-containing leaving group of the photoresist polymer may beremoved by the active fluorine. A hydroxyl group or a carboxylic groupmay be created at a site from which the silicon-containing leaving groupis removed. Thus, the exposed portion may have hydrophilicity and/orsolubility greater than those of a non-exposed portion. Accordingly, theexposed portion may be selectively removed by an etching process or adeveloping process to form a photoresist pattern.

According to example embodiments as described above, a photoresistcomposition includes a photo-fluorine generator. The photo-fluorinegenerator may generate active fluorine such as the fluorine ion, ratherthan using a PAG to create acid in which mobility and diffusion are noteasily controlled. Thus, a photoresist pattern having desired (orpredetermined) line width and/or pitch may be formed from thephotoresist composition. Further, the sulfonium fluoride may be used asthe photo-fluorine generator to facilitate the generation of the activefluorine, and the sensitizer may be added to implement aphoto-lithography system with a high sensitivity.

FIGS. 1 to 6 are cross-sectional views for reference in describing amethod of manufacturing a patterned device in accordance with exampleembodiments. In the example of FIGS. 1 to 6, a patterned device isobtained utilizing the photoresist compositions of the previous exampleembodiments described above.

Referring to FIG. 1, an object layer 110 may be formed on a substrate100. The substrate 100 may be a semiconductor substrate (such as asubstrate completely formed of semiconductor material, or asemiconductor-on-insulator substrate). For example, the substrate 100may include a silicon substrate, a germanium substrate, asilicon-germanium substrate, a silicon-on-insulator (SOI) substrate or agermanium-on-insulator (GOI) substrate. In example embodiments, thesubstrate 100 includes a group III-V compound such as GaP, GaAs or GaSb.

An image may be transferred from a photoresist pattern to the objectlayer 110 so that the object layer 110 may be converted to a desired (orpredetermined) pattern. In some embodiments, the object layer 110 may beformed of an insulative material such as silicon oxide, silicon nitrideor silicon oxynitride. In some embodiments, the object layer 110 may beformed of a conductive material such as a metal, a metal nitride, ametal silicide or a metal silicide nitride. In some embodiments, theobject layer 110 may be formed of a semiconductor material such aspolysilicon.

The object layer 110 may be formed by at least one deposition process.For example, the objection layer 110 may be formed using at least one ofa chemical vapor deposition (CVD) process, a plasma enhanced chemicalvapor deposition (PECVD) process, a low pressure chemical vapordeposition (LPCVD) process, a high density plasma chemical vapordeposition (HDP-CVD) process, a spin coating process, a sputteringprocess, an atomic layer deposition (ALD) process, or a physical vapordeposition (PVD) process.

Referring to FIG. 2, a lower coating layer 120 and a photoresist layer130 may be formed sequentially on the object layer 110.

The lower coating layer 120 may serve as an adhesive layer for improvingan adhesion between the photoresist layer 130 and the object layer 110,or a planarization layer. In some embodiments, the lower coating layer120 may be formed as an organic-based or inorganic-based anti-reflectivelayer. In some embodiments, the lower coating layer 120 is formed of apolymer which is substantially the same as or similar to the photoresistpolymers as described above.

In some embodiments, the formation of the lower coating layer 120 isomitted.

The photoresist composition according to example embodiments asdescribed above may be coated on the lower coating layer 120 by, forexample, a spin coating process, and may be preliminarily cured by asoft-baking process to form the photoresist layer 130.

According to the example embodiments described above, the photoresistcomposition includes a photoresist polymer, a photo-fluorine generatorand a solvent. In some other example embodiments, the photoresistcomposition further includes the sensitizer.

Referring to FIG. 3, an exposure process may be performed on thephotoresist layer 130.

In example embodiments, an exposure mask 140 is placed on thephotoresist layer 130, and a light may be irradiated through an openingor a transmission portion included in the exposure mask 140.Non-limiting examples of a light source used in the exposure process mayinclude ArF, KrF, an electron beam, I-line or EUV. In exampleembodiments, an EUV light source is utilized in the exposure process.

The photoresist layer 130 may be divided into an exposed portion 133 anda non-exposed portion 135. In example embodiments, a chemical structurein the exposed portion 133 is modified through a Reaction Schememechanism described next. However, the inventive concepts are notlimited by the reaction mechanism dividing the exposed portion 133 andthe non-exposed portion 135.

For example, in the Reaction Scheme, the silicon-containing leavinggroup may be connected to the back-bone chain of the photoresist polymervia two ester groups as represented by Chemical Formula 4, and thesensitizer repeating unit may be also connected to the back-bone chainof the photoresist polymer as represented by Chemical Formula 7.

Referring to Reaction Scheme, when the exposure process may be performedusing the EUV light source, in operation S10, a rearrangement of aphenyl ring may occur in the sulfonic fluoride serving as thephoto-fluorine generator. Accordingly, one phenyl ring may substitutefor hydrogen of another adjacent phenyl ring to create HF.

In the sensitizer repeating unit, a resonance stabilization may occur ina benzene ring and the unshared electron pair of a hydroxyl group by aphoton introduced from the EUV light source to generate a secondaryelectron. Accordingly, at least one fluorine ion (F⁻) may be generatedfrom the sensitizer repeating unit.

In operation S20, a fluorine ion generated from HF and/or the fluorineion generated from the sensitizer repeating unit may attack a siliconatom of the silicon-containing leaving group. For example, the siliconatom may be combined to two fluorine ions to be separated or deprotectedfrom the photoresist polymer.

In operation S30, the ester group from which the silicon-containinggroup may be removed may accept a proton (H⁺) from HF formed by thesulfonic fluoride so that a carboxylic acid may be formed. Thus, theexposed portion 133 may have the hydrophilicity and/or the polaritygreater than those of the non-exposed portion 135.

As described with reference to the above Reaction Scheme, two carboxylicacids may be created by one silicon-containing leaving group, and thusthe hydrophilicity and/or the polarity of the exposed portion 133 may befurther increased.

The EUV light source may have a relatively small wavelength, and may beadvantageous for forming a pattern of a fine pitch and a narrow linewidth. The exposure process may be performed by a reduced power usingthe EUV light source. However, as the power of the EUV light sourcebecomes smaller, a quantity of photons may be also reduced to cause areduction of a sensitivity in a photo-lithography process.

However, according to example embodiments as described above, an activefluorine such as the fluorine ion may be generated even by a relativelysmall quantity of photons due to the rearrangement reaction occurring inthe photo-fluorine generator. The fluorine ions may be further createdfrom the sensitizer or the sensitizer repeating unit through theresonance stabilization. Therefore, a photo-lithography process systemhaving a high sensitivity may be realized. By not generating of an acidfrom a conventional PAG, a reduction of resolution and a pattern defectcaused by an irregular mobility of the acid and/or a diffusion of theacid to the non-exposed portion 135 may be avoided.

Referring to FIG. 4, the exposed portion 133 of the photoresist layer130 may be selectively removed. Accordingly, a photoresist pattern 150may be defined by the non-exposed portion 135 remaining on the objectlayer 110 or the lower coating layer 120.

In example embodiments, the exposed portion 133 are selectively removedusing a developer solution such as an alcohol-based solution, or ahydroxide-based solution including, for example, tetra methyl ammoniumhydroxide (TMAH).

As described with reference to the above Reaction Scheme, the exposedportion 133 may be converted to a pattern which may be significantlypolar and/or hydrophilic relative to the non-exposed portion 135.Therefore, the exposed portion 133 may have a high solubility for thedeveloper solution relatively to the non-exposed portion 135, and thusmay be selectively removed by the developer solution such as TMAH.

In some embodiments, the exposed portion 133 may be removed by a dryetching process. The dry etching process may include a plasma etchingprocess or a reactive ion etching (RIE) process using, for example, anoxygen gas.

The exposed portion 133, as described above, may include a highlyhydrophilic and/or polar group such as carboxylic acid. Thus, theexposed portion 133 may have a relatively high affinity for the plasmaetching process or the RIE process. Therefore, the exposed portion 133may be selectively removed with a high etching selectivity relative tothe non-exposed portion 135.

In some embodiments, a hard-baking process may be performed afterremoving the exposed portion 133 to form the photoresist pattern 150from the non-exposed portion 135.

Referring to FIG. 5, the lower coating layer 120 and the object layer110 may be etched using the photoresist pattern 150 as an etching mask.Accordingly, a lower coating pattern 125 and a target pattern 115 may beformed between the photoresist pattern 150 and the substrate 100.

The etching process may include a dry etching process and/or a wetetching process properly selected in consideration of an etchingselectivity between the photoresist pattern 150 and the object layer110.

In some embodiments, the dry etching process may include a plasmaetching process.

In some embodiments, when performing the wet etching process, a properetchant solution such as fluoric acid, phosphoric acid, sulfuric acid orperoxide may be selected depending on a material included in the objectlayer 110.

In some example embodiments, the lower coating layer 120 is removedduring, for example, the developing process for removing the exposedportion 133 to form the lower coating pattern 125. For example, thefluorine ion created in the exposed portion 133 may be diffused to aportion of the lower coating layer 120 under the exposed portion 133.Accordingly, while removing the exposed portion 133, the portion of thelower coating layer 120 under the exposed portion 133 may beconcurrently removed.

FIGS. 2 through 5 represent example embodiments of intermediate productsin the course of manufacturing a patterned device. Here, theintermediate products include the substrate 100, the object layer 110,the lower coating layer 120, and the photoresist layer 130 (or 135 or150). In some embodiments, however, the formation of the lower coatinglayer 120 is omitted as was mentioned previously.

Referring to FIG. 6, the photoresist pattern 150 and the lower coatingpattern 125 may be removed such that the target pattern 115 may remainon the substrate 100.

In example embodiments, the photoresist pattern 150 and the lowercoating pattern 125 are removed by an ashing process and/or a stripprocess. In some other embodiments, the photoresist pattern 150 and thelower coating pattern 125 are removed by a planarization process, forexample, a chemical mechanical polish (CMP) process.

If the object layer 110 includes a conductive material, the targetpattern 115 may serve as a wiring, a contact, a pad, a plug, aninterconnection structure, or the like of a semiconductor device.

If the object layer 110 includes an insulative material, the targetpattern 115 may serve as a desired (or predetermined) insulationpattern, for example, an insulating interlayer pattern, a fillinginsulation pattern, or the like. In some embodiments, a portion of theobject layer 110 removed by the above-mentioned photolithography processmay be converted into a contact hole, an opening or a trench included inthe insulation pattern.

FIGS. 7 to 13 cross-sectional views illustrating a method of forming apattern in accordance with example embodiments.

For example, FIGS. 7 to 13 illustrate a method of forming a wiringstructure utilizing the above-mentioned photoresist composition.Detailed descriptions on processes and/or materials substantially thesame as or similar to those illustrated with reference to FIGS. 1 to 6are omitted herein.

Referring to FIG. 7, a lower contact 215 extending through a lowerinsulation layer 210 may be formed. A plurality of the lower contacts215 may be formed in the lower insulation layer 210.

In example embodiments, the lower insulation layer 210 is formed on apassivation layer 200, and a contact hole extending through the lowerinsulation layer 210 and the passivation layer 200 may be formed. Thelower contact 215 may be formed by filling a conductive layer in thecontact hole by a deposition process or a plating process.

In some embodiments, the method of forming the pattern in accordancewith example embodiments as described with reference to FIGS. 1 to 6 maybe implemented for the formation of the contact hole using the lowerinsulation layer 210 as an object layer.

The lower insulation layer 210 may be formed of an insulative materialsuch as silicon oxide or silicon oxynitride. For example, the lowerinsulation layer 210 may be formed of a silicon oxide-based materialsuch as plasma enhanced oxide (PEOX), tetraethyl orthosilicate (TEOS),silicate glass, or the like.

The passivation layer 200 may be formed of silicon nitride. Theconductive layer may be formed of a metal such as aluminum (Al),tungsten (W) or copper (Cu), a metal nitride, a metal silicide and/ordoped polysilicon.

In some embodiments, the lower contact 215 may be electrically connectedto a circuit device or a lower wiring formed on a semiconductorsubstrate. Damages of the circuit device or the lower wiring whileforming the contact hole may be limited and/or prevented by thepassivation layer 200.

A first etch-stop layer 220 may be formed on the lower insulation layer210 to cover the lower contacts 215. The first etch-stop layer 220 maybe formed of silicon nitride or silicon oxynitride. For example, thefirst etch-stop layer 220 may be formed by, for example, a CVD process,a PECVD process, a sputtering process or an ALD process.

Referring to FIG. 8, an insulating interlayer 225, a buffer layer 230and a second etch-stop layer 235 may be sequentially formed on the firstetch-stop layer 220.

For example, the insulating interlayer 225 may be formed of theabove-mentioned silicon oxide-based material, or a low dielectric(low-k) oxide such as polysiloxane or silesquioxane. The buffer layer230 and the second etch-stop layer 235 may be formed of, for example,silicon oxynitride and silicon nitride, respectively. A stress generatedfrom the second etch-stop layer 235 may be alleviated or absorbed by thebuffer layer 230.

The insulating interlayer 225, the buffer layer 230 and the secondetch-stop layer 235 may be formed by a deposition process such as a CVDprocess, a PECVD process or a sputtering process such as an ion beamsputtering process, or a spin coating process, etc.

Referring to FIG. 9, a photoresist layer 240 may be formed on the secondetch-stop layer 235.

The photoresist layer 240, as described in FIG. 2, may be formed usingthe photoresist composition according to example embodiments asdescribed above. In some embodiments, a lower coating layer may befurther formed before forming the photoresist layer 240.

The photoresist composition may include the photoresist polymer, thephoto-fluorine generator and the solvent. In some example embodiments,the photoresist composition further includes the sensitizer.

The photo-fluorine generator may include the sulfonium fluoride asrepresented by, for example, the Chemical Formula 1 above. Thephotoresist polymer may include the repeating unit that may include thesilicon-containing leaving group. The repeating unit may be representedby, for example, the Chemical Formula 2 or Chemical Formula 3 above. Thesilicon-containing leaving group may be combined to a back-bone chain ofthe photoresist polymer via at least two linker groups as represented bythe Chemical Formula 4 above.

The sensitizer, as represented by the Chemical Formulae 5 and 6 above,may include an aromatic compound including a fluorine substituent and asubstituent containing an unshared electron pair. In some exampleembodiments, the sensitizer is coupled to the photoresist polymer as asensitizer repeating unit as represented by the Chemical Formula 7above.

The photoresist composition may be coated to form a preliminaryphotoresist layer, and the preliminary photoresist layer may bethermally cured by, for example, a soft-baking process to form thephotoresist layer 240.

Referring to FIG. 10, processes substantially the same as or similar tothose illustrated with reference to FIGS. 3 and 4 may be performed toform a photoresist pattern 250.

In example embodiments, an exposure process using, for example, an EUVlight source is performed to generate an active fluorine such as afluorine ion from the photo-fluorine generator included in an exposedportion. The fluorine ion may be transferred to the silicon-containingleaving group. Accordingly, a photo-chemical reaction may be induced by,for example, the above described Reaction Scheme, so that hydrophilicityand/or polarity of the exposed portion may be significantly increasedrelative to a non-exposed portion. Additionally, sensitivity in theexposed portion may be further enhanced by the sensitizer or thesensitizer repeating unit capable of releasing fluorine ions.

Subsequently, the exposed portion may be selectively removed by adeveloping process or a dry etching process such that the photoresistpattern 250 may be formed.

Referring to FIG. 11, the second etch-stop layer 235, the buffer layer230, the insulating interlayer 225 and the first etch-stop layer 220 maybe partially and sequentially etched using the photoresist pattern 250as an etching mask. Thus, an opening 260 through which the lower contact215 may be exposed may be formed.

The opening 260 may be formed by a dry etching process. The opening 260may extend through the insulating interlayer 225 and the first etch-stoplayer 220, and may at least partially expose an upper surface of thelower contact 215.

In some embodiments, the opening 260 may have a contact hole shapethrough which each lower contact 215 may be exposed. In someembodiments, the opening 260 may have a linear shape through which aplurality of the lower contacts 215 may be exposed.

Referring to FIG. 12, a conductive layer 270 filling the openings 260may be formed.

In example embodiments, a barrier layer 265 is formed conformally alongtop surfaces and sidewalls of the photoresist pattern 250, and sidewallsand bottoms of the openings 260 (or the exposed upper surfaces of thelower contacts 215). The conductive layer 270 may be formed on thebarrier layer 265 to sufficiently fill the openings 260.

The barrier layer 265 may be formed of a metal nitride such as titaniumnitride, tantalum nitride or tungsten nitride. The barrier layer 265 maylimit and/or prevent a metal ingredient in the conductive layer 270 frombeing diffused into the insulating interlayer 225. The barrier layer 265may also provide an adhesion for the formation of the conductive layer270. The barrier layer 265 may be formed by, for example, a sputteringprocess or an ALD process.

The conductive layer 270 may be formed by, for example, anelectroplating process. In this case, a seed layer may be formedconformally on the barrier layer 265 by a sputtering process using acopper target. A plating solution such as a copper sulfate solution maybe used to induce an electrochemical reaction on the seed layer so thatthe conductive layer 270 including copper may be grown or precipitatedon the seed layer.

In some embodiments, the conductive layer 270 may be deposited by asputtering process using a metal target such as copper, tungsten oraluminum, or an ALD process.

Referring to FIG. 13, upper portions of the conductive layer 270 and thebarrier layer 265 may be planarized to form a conductive pattern 280.

In example embodiments, the upper portions of the conductive layer 270and the barrier layer 265 are planarized by a CMP process until a topsurface of the insulating interlayer 225 is exposed. The photoresistpattern 250, the second etch-stop layer 235 and the buffer layer 230 maybe also removed by the planarization process.

Accordingly, the conductive pattern 280 electrically connected to thelower contact 215 may be formed in the opening 260. The conductivepattern 280 may include a barrier pattern 267 formed on the sidewall andthe bottom of the opening 260, and a conductive filling pattern 275filling a remaining portion of the opening 260 on the barrier pattern267.

FIGS. 12 and 13 illustrate that the photoresist pattern 250 is removedby the planarization process for the formation of the conductive pattern280. However, the photoresist pattern 250 may be removed after formingthe opening 260 and before forming the barrier layer 265. For example,after forming the opening 260, the photoresist pattern 250 may beremoved by an ashing process and/or a strip process.

In some embodiments, a wiring electrically connected to the conductivepattern 280 may be further formed on the insulating interlayer 225. Forexample, a metal layer may be formed on the insulating interlayer 225and the conductive pattern 280. The metal layer may be patterned by aphoto-lithography process utilizing the photoresist compositionaccording to example embodiments as described above to form the wiring.

FIGS. 14 to 35 are top plan views and cross-sectional views illustratinga method of manufacturing a semiconductor device in accordance withexample embodiments. For example, FIGS. 14 to 35 illustrate a method ofmanufacturing a logic semiconductor device. For example, the logicsemiconductor device may include a fin field-effect transistor (FinFET).

Specifically, FIGS. 14, 16 and 22 are top plan views illustrating themethod. FIGS. 15, 17 and 18 are cross-sectional views taken along a lineI-I′ indicated in the top plan views. FIGS. 20, 24, 26 and 30 includecross-sectional views taken along lines I-I′ and II-II′ indicated in thetop plan views. FIGS. 19, 21, 23, 25, 27 to 29, and 31 to 35 arecross-sectional views taken along a line indicated in the top planviews.

Two directions substantially parallel to a top surface of a substrateand crossing each other may be defined as a first direction and a seconddirection in FIGS. 14 to 35. For example, the first and seconddirections may be perpendicular to each other. A direction indicated byan arrow and a reverse direction thereof are considered as the samedirection.

Referring to FIGS. 14 and 15, an active pattern 305 protruding from asubstrate 300 may be formed.

The substrate 300 may include a semiconductor material such as Si, Ge,Si—Ge, or a group III-V compound such as InP, GaP, GaAs, GaSb, etc. Insome embodiments, the substrate 300 may include an SOI substrate or aGOI substrate.

In example embodiments, the active pattern 305 is formed by a shallowtrench isolation (STI) process. For example, an upper portion of thesubstrate 300 may be partially etched to form an isolation trench, andthen an insulation layer sufficiently filling the isolation trench maybe formed on the substrate 300. An upper portion of the insulation layermay be planarized by, for example, a CMP process until a top surface ofthe substrate 300 may be exposed to form an isolation layer 302. Theinsulation layer may be formed of, for example, silicon oxide.

A plurality of protrusions defined by the isolation layer 302 may beformed from the substrate 300. The protrusions may be defined as theactive patterns 305. The active pattern 305 may extend linearly in thefirst direction, and a plurality of the active patterns 305 may beformed along the second direction.

In some embodiments, an ion-implantation process may be performed toform a well at an upper portion of the active pattern 305.

In some embodiments, the active pattern 305 may be formed from anadditional channel layer. In this case, the channel layer may be formedon the substrate 300 by, for example, a selective epitaxial growth (SEG)process, and an STI process may be performed on the channel layer toform the active pattern 305.

Referring to FIGS. 16 and 17, an upper portion of the isolation layer302 may be removed by, for example, an etch-back process so that anupper portion of the active pattern 305 may be exposed. The upperportion of the active pattern 305 exposed from a top surface of theisolation layer 302 may be defined as an active fin 307. The active fin307 may extend in the first direction, and a plurality of the activefins 207 may be arranged along the second direction.

Referring to FIGS. 18 and 19, a dummy gate insulation layer 310, a dummygate electrode layer 312 and a dummy gate mask layer 316 may besequentially formed on the active fin 307 and the isolation layer 302. Afirst photoresist layer 320 may be formed on the dummy gate mask layer316.

The dummy gate insulation layer may be formed of silicon oxide. Thedummy gate electrode layer may be formed of polysilicon. The dummy gatemask layer may be formed of silicon nitride. The dummy gate insulationlayer, the dummy gate electrode layer and the dummy gate mask layer maybe formed by a CVD process, a sputtering process or an ALD process.

The first photoresist layer 320, as described in FIG. 2, may be formedusing the photoresist composition according to example embodiments. Insome embodiments, a lower coating layer is further formed before formingthe first photoresist layer 320.

The photoresist composition may include the photoresist polymer, thephoto-fluorine generator and the solvent. In some example embodiments,the photoresist composition further includes the sensitizer.

The photo-fluorine generator may include the sulfonium fluoride asrepresented by, for example, the Chemical Formula 1 above. Thephotoresist polymer may include the repeating unit that may include thesilicon-containing leaving group. The repeating unit may be representedby, for example, the Chemical Formula 2 or Chemical Formula 3 above. Thesilicon-containing leaving group may be combined to a back-bone chain ofthe photoresist polymer via at least two linker groups as represented bythe Chemical Formula 4 above.

The sensitizer, as represented by the Chemical Formulae 5 and 6 above,may include an aromatic compound including a fluorine substituent and asubstituent containing an unshared electron pair. In some exampleembodiments, the sensitizer is coupled to the photoresist polymer as asensitizer repeating unit as represented by the Chemical Formula 7above.

A preliminary photoresist layer may be formed by coating the photoresistcomposition, and then a thermal curing process, for example, asoft-baking process may be performed thereon to form the firstphotoresist layer 320.

Referring to FIGS. 20 and 21, a dummy gate structure 319 may be formedby a photo-lithography process using the first photoresist layer 320.

In example embodiments, processes that are substantially the same as orsimilar to those previously described with reference to FIGS. 3 and 4are performed to form a first photoresist pattern 325.

For example, an exposure process using, for example, an EUV light sourcemay be performed to generate an active fluorine such as a fluorine ionfrom the photo-fluorine generator included in an exposed portion. Thefluorine ion may be transferred to the silicon-containing leaving group.Accordingly, a photo-chemical reaction may be induced by, for example,the above Reaction Scheme, so that a hydrophilicity and/or a polarity ofthe exposed portion may be significantly increased relative to anon-exposed portion. Additionally, sensitivity in the exposed portionmay be further enhanced by the sensitizer or the sensitizer repeatingunit capable of releasing fluorine ions.

The exposed portion may be selectively removed by a developing processor a dry etching process to form the first photoresist pattern 325.

The dummy gate mask layer 316, the dummy gate electrode layer 312 andthe dummy gate insulation layer 310 may be sequentially etched using thefirst photoresist pattern 325 as an etching mask. After the etchingprocess, a dummy gate structure 319 including a dummy gate insulationpattern 311, a dummy gate electrode 315 and a dummy gate mask 317sequentially stacked from the active fin 307 and the isolation layer 302may be formed.

The dummy gate structure 319 may extend in the second direction, and maycross a plurality of the active fins 307. A plurality of the dummy gatestructures 319 may be formed along the first direction.

The first photoresist pattern 325 may be removed by an ashing processand/or a strip process after forming the dummy gate structure 319.

Referring to FIGS. 22 and 23, a gate spacer 330 may be formed on asidewall of the dummy gate structure 319.

In example embodiments, a spacer layer is formed on the dummy gatestructure 319, the active fin 307 and the isolation layer 302, and thespacer layer may be anisotropically etched to form the gate spacer 330.The spacer layer may be formed of a nitride, for example, siliconnitride, silicon oxynitride, silicon carbonitride, and so on.

As illustrated in FIG. 22, the gate spacer 330 may extend in the seconddirection together with the dummy gate structure 319.

Referring to FIGS. 24 and 25, an upper portion of the active fin 307adjacent to the gate spacer 330 and/or the dummy gate structure 319 maybe etched to form a recess 335.

In the etching process for the formation of the recess 335, the gatespacer 330 may substantially serve as an etching mask. In exampleembodiments, an inner wall of the recess 335 have a substantially“U”-shaped profile as illustrated in FIG. 25.

In some embodiments, the recess 335 may extend to a portion of theactive pattern 305 below the top surface of the isolation layer 302.

Referring to FIGS. 26 and 27, a source/drain layer 340 filling therecess 335 may be formed.

In example embodiments, the source/drain layer 340 is formed by an SEGprocess using the top surface of the active fin 307 exposed by therecess 335 as a seed.

In some embodiments, an n-type impurity source such as phosphine (PH₃)or a p-type impurity source such as diborane (B₂H₆) may be providedtogether with a silicon source such as silane in the SEG process.

The source/drain layer 340 may be grown vertically and laterally tohave, for example, a polygonal cross-section as illustrated in FIG. 26.In some embodiments, the source/drain layer 340 may sufficiently fillthe recess 335 to contact a lower portion of the gate spacer 330.

Referring to FIG. 28, a lower insulation layer 345 covering the dummygate structure 319, the gate spacer 330 and the source/drain layers 340may be formed on the active fin 307 and the isolation layer 302. Anupper portion of the lower insulation layer 345 may be planarized by aCMP process and/or an etch-back process until a top surface of the dummygate electrode 315 may be exposed.

In some embodiments, the dummy gate mask 317 may be removed by the CMPprocess, and an upper portion of the gate spacer 330 may be alsopartially removed.

The lower insulation layer 345 may be formed of, for example, a siliconoxide-based material by a CVD process.

Referring to FIG. 29, the dummy gate electrode 315 and the dummy gateinsulation pattern 311 may be removed. Accordingly, a trench (notillustrated) exposing an upper portion of the active fin 307 may beformed between a pair of the gate spacers 330.

The exposed active fin 307 may be thermally oxidized to form aninterface layer 350. A gate insulation layer 352 may be formed along atop surface of the lower insulation layer 345, an inner wall of thetrench, and top surfaces of the interface layer 350 and the isolationlayer 302, and a buffer layer 354 may be formed on the gate insulationlayer 352. A gate electrode layer 356 filling a remaining portion of thetrench may be formed on the buffer layer 354.

The gate insulation layer 352 may be formed of a metal oxide having ahigh dielectric constant (high-k) such as hafnium oxide, tantalum oxideand/or zirconium oxide. The buffer layer 354 may be included foradjusting a work function of a gate electrode. The buffer layer 354 maybe formed of a metal nitride such as titanium nitride, tantalum nitrideand/or aluminum nitride. The gate electrode layer 356 may be formed of ametal having a low electric resistance such as aluminum, copper,tungsten, or the like.

The gate insulation layer 352, the buffer layer 354 and the gateelectrode layer 356 may be formed by a CVD process, an ALD process, aPVD process, etc. In some embodiments, the interface layer 350 may bealso formed by a deposition process such as a CVD process or an ALDprocess. In this case, the interface layer 350 may have a profilesubstantially the same as or similar to that of the gate insulationlayer 352.

Referring to FIGS. 30 and 31, upper portions of the gate electrode layer356, the buffer layer 354 and the gate insulation layer 352 may beplanarized by, for example, a CMP process until the top surface of thelower insulation layer 345 may be exposed.

After the planarization process, a gate structure including theinterface layer 350, a gate insulation pattern 351, a buffer pattern 353and a gate electrode 357 may be defined in the trench. An NMOStransistor or a PMOS transistor having a FinFET structure may be definedby the gate structure and the source/drain layer 340.

A passivation layer 360 may be formed on the lower insulation layer 345,the gate spacers 330 and the gate structure. The passivation layer 360may be formed of a nitride-based material such as silicon nitride orsilicon oxynitride by a CVD process. A portion of the passivation layer360 covering the gate structure may serve as a gate mask.

Referring to FIG. 32, an active contact 365 electrically connected tothe source/drain layer 340 may be formed.

In example embodiments, the passivation layer 360 and the lowerinsulation layer 345 are partially etched to form a first contact holethrough which the source/drain layer 340 may be exposed.

In some embodiments, while performing the etching process for formingthe first contact hole, an upper portion of the source/drain layer 340is partially removed.

In example embodiments, a silicide pattern 343 is formed at the upperportion of the source/drain layer 340 exposed through the first contacthole. For example, a metal layer may be formed on the source/drain layer340 exposed through the first contact hole, and then a thermal treatmentsuch as an annealing process may be performed thereon. A portion of themetal layer contacting the source/drain layer 340 may be transformedinto a metal silicide by the thermal treatment. An unreacted portion ofthe metal layer may be removed to form the silicide pattern 343.

The metal layer may be formed of, for example, cobalt or nickel. Thesilicide pattern 343 may include, for example, cobalt silicide or nickelsilicide.

In some embodiments, the silicide pattern 343 may protrude from a topsurface of the source/drain layer 340 to fill a lower portion of thefirst contact hole.

Subsequently, an active contact 365 filling the first contact hole maybe formed. For example, a conductive layer sufficiently filling thefirst contact holes may be formed on the passivation layer 360. An upperportion of the conductive layer may be planarized by a CMP process untila top surface of the passivation layer 360 may be exposed to form theactive contacts 365. The conductive layer may be formed of a metal, ametal nitride, a metal silicide or a doped polysilicon.

In some embodiments, a gate contact 367 may be formed on the gatestructure. The gate contact 367 may be formed through the passivationlayer 360 to be in contact with a top surface of the gate electrode 357.

In some embodiments, the gate contact 367 and the active contact 365 maybe formed by substantially the same etching process and depositionprocess. For example, a second contact hole exposing the top surface ofthe gate electrode 357 may be formed through passivation layer 360together with the first contact hole. The conductive layer may also fillthe second contact hole, and the gate contact 367 may be formed in thesecond contact hole by the CMP process.

Subsequently, a back-end-of-line (BEOL) process for forming a routingcircuit of the logic semiconductor device may be performed.

Referring to FIG. 33, a first insulating interlayer 370 may be formed onthe passivation layer 360, the active contact 365 and the gate contact367. A second photoresist pattern 375 may be formed on the firstinsulating interlayer 370.

In example embodiments, a second photoresist layer is formed on thefirst insulating interlayer 370 from a material and a process that issubstantially the same as or similar to those for forming the firstphotoresist layer 320 previously described with reference to FIGS. 18and 19.

The second photoresist layer may be formed using the photoresistcomposition according to example embodiments as described above.

Subsequently, processes that are substantially the same as or similar tothose previously described with reference to FIGS. 3 and 4 may beperformed to form the second photoresist pattern 375.

For example, an exposure process using, for example, an EUV light sourcemay be performed to generate an active fluorine such as a fluorine ionfrom a photo-fluorine generator included in an exposed portion of thesecond photoresist layer. The fluorine ion may be transferred to asilicon-containing leaving group of a photoresist polymer. Accordingly,a photo-chemical reaction may be induced by, for example, the aboveReaction Scheme, so that a hydrophilicity and/or a polarity of theexposed portion may be significantly increased relative to a non-exposedportion. Additionally, sensitivity in the exposed portion may be furtherenhanced by a sensitizer or a sensitizer repeating unit capable ofreleasing fluorine ions.

The exposed portion may be selectively removed by a developing processor a dry etching process to form the second photoresist pattern 375.

Referring to FIG. 34, the first insulating interlayer 370 may bepartially removed using the second photoresist pattern 375 as an etchingmask to form a first opening through which the active contact 365 may beexposed. The first opening may be filled with a conductive material toform a first wiring 372 electrically connected to the active contact365.

Referring to FIG. 35, a second insulating interlayer 380 covering thefirst wirings 372 may be formed on the first insulating interlayer 370.The first and second insulating interlayers 370 and 380 may be formed ofa low-k polysiloxane or silesquioxane-based oxide by a CVD process, aspin coating process, etc.

A second opening extending through the second insulating interlayer 380and the first insulating interlayer 370 may be formed such that a topsurface of the gate contact 367 may be exposed. The second opening maybe formed by processes substantially the same as or similar to thosedescribed with reference to FIGS. 33 and 34.

For example, the second opening may be formed using a photo-lithographyprocess system with an improved sensitivity based on a photo-fluorinegenerator according to example embodiments as described above.

A through contact 385 electrically connected to the gate contact 367 maybe formed by filling the second opening with a conductive material.

A metal layer may be formed on the second insulating interlayer 380 tocover the through contact 385. The metal layer may be patterned to forma second wiring 390 electrically connected to the through contact 385.

The second wiring 390 may be also formed by the photo-lithographyprocess system based on the photo-fluorine generator according toexample embodiments.

As described above, according to example embodiments of a photoresistcomposition of the present inventive concepts, a photo-fluorinegenerator creating a fluorine ion is used instead of a photo-acidgenerator (PAG). However, it is noted that not all embodiments of theinventive concepts are limited to photoresist compositions devoid ofPAG. That is, the photoresist compositions of some embodiments may bedevoid of PAG, and the photoresist compositions of other embodiment mayinclude PAG.

The photo-fluorine generator may include a sulfonium fluoride, and ageneration of the fluorine ion may be facilitated by a sulfonium group.The fluorine ion may attack, for example, a silicon-containing leavinggroup contained in a photoresist polymer. Accordingly, hydrophilicityand/or polarity of an exposed portion of the photoresist polymer may beincreased, and the exposed portion may be selectively removed by adeveloping process. Further, a repeating unit or a compound capable ofphoto-chemically generating a plurality of fluorine ions may be used asa sensitizer to amplify the generation of the fluorine ions. Therefore,a photo-lithography process system with a high sensitivity may berealized without an intervention of an acid.

The photoresist composition may be utilized in a photo-lithographyprocess for forming a fine pattern having a critical dimension below,for example, about 20 nm or about 10 nm. Wirings, contacts, insulationpatterns, and so on, having fine dimensions of various semiconductordevices may be formed using the photo-lithography process.

The foregoing is illustrative of example embodiments and is not to beconstrued as limiting thereof. Although a few example embodiments havebeen described, those skilled in the art will readily appreciate thatmany modifications are possible in the example embodiments withoutmaterially departing from the novel teachings and advantages of thepresent inventive concept. Accordingly, all such modifications areintended to be included within the scope of the present inventiveconcept as defined in the claims. In the claims, means-plus-functionclauses are intended to cover the structures described herein asperforming the recited function and not only structural equivalents butalso equivalent structures. Therefore, it is to be understood that theforegoing is illustrative of various example embodiments and is not tobe construed as limited to the specific example embodiments disclosed,and that modifications to the disclosed example embodiments, as well asother example embodiments, are intended to be included within the scopeof the appended claims.

What is claimed is:
 1. A method of manufacturing a patterned device,comprising: forming an object layer on a substrate; forming aphotoresist layer on the object layer by coating the object layer with aphotoresist composition, the photoresist composition comprising aphotoresist polymer including a repeating unit to which asilicon-containing leaving group is combined, a photo-fluorine generatorincluding a sulfonium fluoride, and a solvent; performing an exposureprocess on the photoresist layer such that the photoresist layerincludes an exposed portion and a non-exposed portion; removing theexposed portion to form a photoresist pattern; and patterning the objectlayer using the photoresist pattern as a mask, wherein thesilicon-containing leaving group is connected to a back-bone chain ofthe photoresist polymer via at last two linker groups.
 2. The method ofclaim 1, wherein performing the exposure process includes separating thesilicon-containing leaving group from the photoresist polymer by afluorine ion created from the photo-fluorine generator in the exposedportion.
 3. The method of claim 2, wherein a hydroxyl group or acarboxylic group is created at a site from which the silicon-containingleaving group of the exposed portion is removed.
 4. The method of claim3, wherein the exposed portion is more hydrophilic or more polar thanthe non-exposed portion.
 5. The method of claim 4, wherein removing theexposed portion includes a developing process using a hydrophilicsolution.
 6. The method of claim 2, wherein the photoresist compositionfurther includes a sensitizer capable of generating fluorine, andwherein performing the exposure process includes separating thesilicon-containing leaving group from the photoresist polymer by afluorine ion created from the sensitizer and the fluorine ion createdfrom the photo-fluorine generator.
 7. The method of claim 6, wherein thesensitizer includes an aromatic compound that includes a fluorinesubstituent and a substituent including an unshared electron pair. 8.The method of claim 1, wherein performing the exposure process includesusing an extreme ultraviolet (EUV) light source.
 9. A method ofmanufacturing a semiconductor device, comprising: forming an isolationlayer on a substrate to define active patterns of the substrate; forminga gate structure on the isolation layer and the active patterns; formingcontacts electrically connected to the active patterns; forming aninsulating interlayer covering the gate structure and the contacts;forming a photoresist layer on the insulating interlayer by coating theinsulating layer with a photoresist composition, the photoresistcomposition comprising a photoresist polymer including a repeating unitto which a silicon-containing leaving group is combined, aphoto-fluorine generator including a sulfonium fluoride, and a solvent;partially removing the photoresist layer to form a photoresist pattern;partially etching the insulating interlayer using the photoresistpattern as a mask to form openings through which the contacts areexposed; and forming wirings in the openings, the wirings beingelectrically connected to the contacts, wherein the silicon-containingleaving group is connected to a back-bone chain of the photoresistpolymer via at least two linker groups.
 10. The method of claim 9,wherein partially removing the photoresist layer to form the photoresistpattern includes: performing an exposure process on the photoresistlayer such that the photoresist layer includes a non-exposed portion andan exposed portion in which the silicon-containing leaving group isremoved from the photoresist polymer by a fluorine ion generated fromthe photo-fluorine generator; and removing the exposed portion from thephotoresist layer.
 11. The method of claim 10, wherein performing theexposure process includes using an extreme ultraviolet (EUV) lightsource.
 12. The method of claim 10, wherein the photoresist compositionfurther includes a sensitizer capable of generating fluorine.
 13. Themethod of claim 12, wherein the exposure process further includesseparating the silicon-containing leaving group from the photoresistpolymer by a fluorine ion created from the sensitizer.